This invention relates to a silver halide photographic light-sensitive material containing a benzyliden or cinnamylidene type dye and particularly to a silver halide photographic light-sensitive material in which a specific layer is dyed with a novel benzylidene or cinnamylidene type dye so that a fog production and an aging desensitization can be reduced.
For silver halide photographic light-sensitive materials, the high image qualities such as an excellent sharpness and an excellent color reproducibility are required.
In recent years, they have also been required to further shorten the processing time, that is, to have an ultrarapid processing aptitude so as to compete with the instant processability of an electrophotographic material. For realizing the high image qualities and the ultrarapid processing aptitude each having been required, the efforts have been made in the industry to make a layer more thinner and to optimize the silver halides and the raw materials such as the compounds to be added in.
For the purposes of improving the image qualities and controlling the sensitivity of a silver halide emulsion, it has been well known that a dye is contained in a silver halide photographic light-sensitive material. For example, such a dye has been used for preventing a halation and irradiation and in a light absorption filter.
Recently, the range of using the dyes has been widely increased, for example, in a dye useful in place of yellow colloidal silver in a color photographic light-sensitive material --hereinafter referred to as a `YC dye`--, a dye for dyeing a crossover-cut layer in an X ray photographic light-sensitive material, and a dye for dyeing a non-light-sensitive emulsion layer in a graphic art photographic light-sensitive material.
For the dyes applicable for the above-mentioned purposes, the following characteristics are required to meet the various purposes:
1. An excellent absorption spectrum is to be provided; PA1 2. No diffusion is to be produced from a dyed layer to the other layers; PA1 3. Any light-sensitive silver halide emulsion is not to be affected photographically; PA1 4. The dye is to be stable in any silver halide photographic light-sensitive material; PA1 5. The dye is to be readily added; PA1 6. The dye is to be stable in any emulsion coating solution and is not to affect any viscosity of the solution; and PA1 7. No color is to remain after a light-sensitive material is processed.
There have been the proposals for numerous dyes so far to satisfy the above-mentioned requirements. For example, there have been the oxonol dyes proposed in British Patent --BP-- No. 506,385 and Japanese Patent Examined Publication --JP EP-- No. 39-22069/1964; the merocyanine dyes proposed in U.S. Pat. No. 2,493,747; and the styryl dyes proposed in U.S. Pat. No. 1,845,404. Besides the above, Japanese Patent Publication Open to Public Inspection --JP OPI-- Nos. 1-196040/1989 and 1-196041/1989 disclose each the arylidene dyes.
The above-given dyes are generally used by dissolving them in either water or a water-miscible organic solvent and then by adding into a photographic component layer. However, if the dye is water-soluble, it does not remain in a subject layer to be dyed, but diffuses into the whole layer. When trying to achieve the original object, therefore, a large quantity of the dye should be added as much as the quantity diffused into the other layers, so that the other layers as well as the subject layer produce the undesirable phenomena such as a lowered sensitivity, a varied gradation and an abnormal fog production. When a light-sensitive material is aged in storage, in particular, a fogging or desensitizing phenomenon is seriously produced. If the quantity of the dye is reduced to avoid the above-mentioned phenomena, the original light-absorption effect cannot satisfactorily be obtained. For solving the above-mentioned problems, there has been the known dyes capable of dyeing a specific layer with inhibiting the diffusibility. As for the antidiffusible type dyes, for example, the YC dyes are described in U.S. Pat. Nos. 2,538,008, 2,539,009, and 4,420,555; and JP OPI Nos. 61-204630/1986, 61-205934/1986, 62-32460/1987, 62-56958/1987, 62-92949/1987, 62-222248/1987, 63-40143/1988, 63-184749/1988, and 63-316852/1988. The above-given dyes have been many proposed to save the valuable natural silver sources and to improve the defects that a color photographic component generally used, that is a yellow colloidal silver so called Carey Lea Silver, lowers a green sensitivity, because the silver absorbs not only blue rays of light but also the other color rays of light from a part of the long wavelength region; and that a fog production is increased in an adjacent layer.
The above-mentioned defects may be improved to some extent by the antidiffusible dyes and, on the other hand, thereby deteriorating a preservability and producing a desensitization in aging and, further, making a bleachability insufficient, so as to cause a new color staining problem. For solving the problem, a further new antidiffusible dye has been demanded.
It is, accordingly, an object of the invention to provide a silver halide photographic light-sensitive material capable of satisfying the above-described requirements for the antidiffusible dyes, reducing the fog production, and being improved in aging stability.
The silver halide photographic light-sensitive materials of the invention comprise each a support provided thereonto with at least one layer containing the fine solid particle dispersing elements of the compound represented by the following formula I:
Formula I EQU A=L.sub.1 -L.sub.2 =L.sub.3).sub.m B
wherein A represents an acidic mother nucleus of 2-pyrazoline-5-one; B represents an aryl group which is substituted at the 4th position thereof with an amino group having at least one substituent selected from a group consisting of alkenyl, alkynyl and heterocyclic groups, or a cyclic amino group; L.sub.1 through L.sub.3 represent each a methine group; m is an integer of 0 or 1; wherein, A is to contain at least either one selected from the group consisting of carboxyphenyl groups, sulfonamidophenyl groups, aminosulfonylaminophenyl groups.
The invention will now be detailed below.
The amino group having at least one substituent substituted at the 4th position of the aryl group represented by B may be mono- or di-substituted amino group. In case of di-substituted amino group one of the substituents may be an alkenyl group, alkynyl group, or a substituent other than a heterocyclic group such as an alkyl, aryl or cycloalkyl.
The alkyl groups include, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-dodecyl group, an n-pentadecyl group and an eicosyl group. The alkyl groups also include those having each a substituent. Such substituents include, for example; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom and a fluorine atom; an aryl group such as a phenyl group, and a naphthyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a heterocyclic group such as a pyrrolidyl group and a pyridyl group; a sulfinic acid group; a carboxyl group; a nitro group; a hydroxyl group; a mercapto group; an amino group such as an amino group and a diethylamino group; an alkyloxy group such as a methyloxy group, an ethyloxy group, an n-butyloxy group, an n-octyloxy group and an isopropyloxy group; an aryloxy carbamoyl group such as an aminocarbonyl group, a methylcarbamoyl group, an n-pentylcarbamoyl group, and a phenylcarbamoyl group; an amido group such as a methylamido group, a benzamido group, and an n-octylamido group; an aminosulfonylamino group such as an aminosulfonylamino group, a methylaminosulfonylamino group, and an anilinosulfonylamino group; a sulfamoyl group such as a sulfamoyl group, a methylsulfamoyl group, a phenylsulfamoyl group, and an n-butylsulfamoyl group; a sulfonamido group such as a methanesulfonamido group, an n-heptanesulfonamido group and a benzenesulfonamido group; a sulfinyl group such as an alkylsulfinyl group including a methylsulfinyl group, an ethylsulfinyl group, and an octylsulfinyl group, and an arylsulfinyl group including a phenylsulfinyl group; an alkyloxycarbonyl group such as a methyloxycarbonyl group, an ethyloxycarbonyl group, a 2-hydroxyethyloxycarbonyl group and an n-octyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group and a naphthyloxycarbonyl group; an alkylthio group such as a methylthio group, an ethylthio group and an n-hexylthio group; an arylthio group such as a phenylthio group and a naphthylthio group; an alkylcarbonyl group such as an acetyl group, an ethylcarbonyl group, an n-butylcarbonyl group and n-octylcarbonyl group; an arylcarbonyl group such as a benzoyl group, a p-methanesulfonamidobenzoyl group, a p-carboxybenzoyl group and a naphthoyl group; a cyano group; a ureido group such as a methylureido group and a phenylureido group; and a thioureido group such as a methylthioureido group and a phenylthioureido group.
The cycloalkyl groups serving as the substituents to the amino groups include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The cycloalkyl groups include those having each a substituent. Such substituents include those exemplified for the alkyl groups and for the substituents to the foregoing alkyl groups.
The aryl groups for serving as the substituents to the amino groups include, for example, a phenyl group and a naphthyl group. Such aryl groups include those having a substituent, and such substituents include those groups exemplified for the foregoing alkyl groups and for the foregoing substituents to the alkyl groups.
The alkenyl groups for serving as the substituents to the amino groups include, for example, a vinyl group, an allyl group, a 1-propenyl group, a 1,3-butadienyl group and a 2-pentenyl group. The alkenyl groups include those having a substituent, and the subsituents include those to the foregoing alkyl groups.
The heterocyclic groups serving as the substituents to the amino groups include, for example; pyridyl groups such as a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 5-carboxy-2-pyridyl group, a 3,5-dichloro-2-pyridyl group, a 4,6-dimethyl-2-pyridyl group, a 6-hydroxy-2-pyridyl group, a 2,3,5,6-tetrafluoro-4-pyridyl group, and a 3-nitro-2-pyridyl group; oxazolyl groups such as a 5-carboxyl-2-benzoxazolyl group, a 2-benzoxazolyl group, and a 2-oxazolyl group; thiazolyl groups such as a 5-sulfamoyl-2-benzthiazolyl group, a 2-benzthiazolyl group, and a 2-thiazolyl group; imidazolyl groups such as a 1-methyl-2-imidazolyl group, and a 1-methyl-5-carboxy-2-benzimidazolyl group; furyl groups such as a 3-furyl group; pyrrolyl groups such as a 3-pyrrolyl group; thienyl groups such as a 2-thienyl group; pyrazinyl groups such as a 2-pyrazinyl group; pyrimidinyl groups such as a 2-pyrimidinyl group, and a 4-chloro-2-pyrimidinyl group; pyridazinyl groups such as a 2-pyridazinyl group; purinyl groups such as a 8-purinyl group; isoxazolyl groups such as a 3-isoxazolyl group; selenazolyl groups such as a 5-carboxy-2-selenazolyl group; sulfolanyl groups such as a 3-sulfolanyl group; pyrazolyl groups such as a 3-pyrazolyl group; and tetrazolyl groups such as a 1-methyl-5-tetrazolyl group. Such heterocyclic groups include those having a substituent and the substituents include those exemplified for the foregoing alkyl groups and for the substituents to the alkyl groups.
The cyclic amino groups include, for example, those removed therefrom a hydrogen atom bonded to a nitrogen atom of piperidine, piperazine or morpholine, and the cyclic amino groups include those having a substituent. The substituents include those exemplified for the foregoing alkyl groups and for the substituents for the alkyl groups.
The aryl components of the aryl groups having at the 4th position thereof a substituted amino group or a cyclic amino group represented by B include, desirably, phenyl. The aryl components include, besides the 4-amino groups, those having a substituent. The substituents include those exemplified for the foregoing alkyl groups and the substituents for the alkyl groups.
The methine groups represented by L.sub.1, L.sub.2 and L.sub.3 include those having a substituent, and the substituents include, for example; alkyl groups such as a methyl group, an ethyl group, a 3-hydroxypropyl group, and a benzyl group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; aryl groups such as a phenyl group; and alkoxy groups such as a methoxy group, and an ethoxy group. Each of these groups includes those having the substituents exemplified for the substituents to the alkyl groups serving as the substituents to the foregoing amino component.
The acidic mother nuclei of 2-pyroazoline-5-one represented by A include those having a substituent. The substituents at the 1st position include, for example, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and a heterocyclic group, and the substituents at the 3rd position include, for example, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carboxyl group, a carbamoyl group, an oxycarbonyl group, an amino group, an amido group, a ureido group, a sulfonamido group, an aminosulfonylamino group, a hydroxy group, an alkyloxy group, an aryloxy group, an acyl group, a cyano group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, a mercapto group, an alkylthio group, and an arylthio group. The alkyl, alkenyl, cycloalkyl, aryl and heterocyclic groups each serving as the substituents at the meta-positions include those exemplified for the substituents to the 4-amino component of the foregoing 4-aminoaryl group, and these substituents include those having such a further substituent as those exemplified for the substituents to the aryl groups serving as the substituents to the foregoing 4-amino component.
The amino groups serving as the substituents at the 3rd position include, for example, an alkylamino group, a dialkylamino group, and an arylamino group. The alkyl and aryl groups include, for example, those exemplified for the alkyl and aryl groups serving as the substituents to the foregoing 4-amino component. They also include those having such a substituent as those exemplified for the substituents to the aryl groups serving as the substituents to the foregoing 4-amino component.
The oxycarbonyl groups serving as the substituents at the 3rd position include, for example, an alkyloxycarbonyl group, an aryloxycarbonyl group and a heterocyclic oxycarbonyl group; the acyl groups include, for example, an alkylcarbonyl group, an arylcarbonyl group and a heterocyclic carbonyl group; the carbamoyl groups include, for example, a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, a heterocyclic carbamoyl group, and a nitrogen-containing hetercyclic carbonyl group such as a 1-piperidinocarbonyl group and a 4-morpholinocarbonyl group. The ureido groups include, for example, an alkylureido group, an arylureido group and a heterocyclic ureido group; the amido groups include, for example, an alkylcarbonylamino group, an arylcarbonylamino group and a heterocyclic carbonylamino group; the sulfonamido groups include, for example, an alkylsulfonylamino group, an arylsulfonylamino group and a heterocyclic sulfonylamino group; the aminosulfonylamino groups include, for example, an alkylaminosulfonylamino group, a dialkylaminosulfonylamino group, an arylaminosulfonylamino group and a heterocyclic aminosulfonylamino group; the sulfamoyl groups include, for example a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group and a heterocyclic sulfamoyl group; the sulfonyl groups include, for example, an alkylsulfonyl group, an arylsulfonyl group and a heterocyclic sulfonyl group; and the sulfinyl groups include, for example, an alkylsulfinyl group, an arylsulfinyl group and a heterocyclic sulfinyl group. The alkyl, aryl and heterocyclic components contained each in the above-given groups, and the alkyl and aryl components contained each in the alkyloxy, aryloxy, alkylthio or arylthio group include, for example, those exemplified for the alkyl, aryl and heterocyclic groups each serving as the substituents to the foregoing 4-amino component, and they include those having such a further substituent as those exemplified for the substituents to the aryl groups serving as the substituents to the foregoing 4-amino component.
The compounds represented by Formula I has a carboxyphenyl group, a sulfonamidophenyl group or an aminosulfonylaminophenyl group. The sulfonamido and aminosulfonylamino groups are each exemplified by each of the groups serving as the substituents at the 3rd position of the acidic mother nuclei of 2-pyrazoline-5-one. The examples includes of a phenyl group having a carboxy group, aminosufonylamino group or a sulfonamide group, includes those having a substituent, whose examples are such substituent as an exemplified group serving as the substituents of the substituted amino group at the 4th position of the aryl group. ##STR1##